Hydraulic cements comprising carbonate compound compositions

ABSTRACT

Hydraulic cement compositions that include a carbonate compound composition, e.g., a salt-water derived carbonate compound composition containing crystalline and/or amorphous carbonate compounds, are provided. Also provided are methods of making and using the hydraulic cements, as well as settable compositions, such as concretes and mortars, prepared therefrom. The cements and compositions produced therefrom find use in a variety of applications, including use in a variety of building materials and building applications.

CROSS-REFERENCE TO RELATED APPLICATIONS

Pursuant to 35 U.S.C. §119 (e), this application claims priority to thefiling dates of: U.S. Provisional Patent Application Ser. No. 60/931,657filed on May 24, 2007; U.S. Provisional Patent Application Ser. No.60/937,786 filed on Jun. 28, 2007; U.S. Provisional Patent Application61/017,419 filed on Dec. 28, 2007 and U.S. Provisional PatentApplication Ser. No. 61/017,371 filed on Dec. 28, 2007, the disclosuresof which applications are herein incorporated by reference.

INTRODUCTION

Concrete is the most widely used engineering material in the world. Itis estimated that the present world consumption of concrete is 11billion metric tons per year. (Concrete, Microstructure, Properties andMaterials (2006, McGraw-Hill)). Concrete is a term that refers to acomposite material of a binding medium having particles or fragments ofaggregate embedded therein. In most construction concretes currentlyemployed, the binding medium is formed from a mixture of a hydrauliccement and water.

Hydraulic cements are compositions which set and harden after combiningwith water. After hardening, the compositions retain strength andstability even under water. The key requirement for this characteristicis that the hydrates formed from the cement constituents upon reactionwith water are essentially insoluble in water. Cements may be employedby themselves or in combination with aggregates, both coarse and fine,in which case the compositions may be referred to as concretes ormortars.

Setting and hardening of hydraulic cements is caused by the formation ofwater-containing compounds, forming as a result of reactions betweencement components and water. The reaction and the reaction products arereferred to as hydration and hydrates or hydrate phases, respectively.As a result of the immediately starting reactions, a stiffening can beobserved which is very small in the beginning, but which increases withtime. After reaching a certain level, this point in time is referred toas the start of setting. The consecutive further consolidation is calledsetting, after which the phase of hardening begins. The compressivestrength of the material then grows steadily, over a period which rangesfrom a few days in the case of “ultra-rapid-hardening” cements, toseveral years in the case of ordinary cements.

Most hydraulic cements employed today are based upon Portland cement.Portland cement is made primarily from limestone, certain clay minerals,and gypsum, in a high temperature process that drives off carbon dioxideand chemically combines the primary ingredients into new compounds. Theenergy required to fire the mixture consumes about 4 GJ per ton ofcement produced.

Because carbon dioxide is generated by both the cement productionprocess itself, as well as by energy plants that generate power to runthe production process, cement production is currently a leading sourceof current carbon dioxide atmospheric emissions. It is estimated thatcement plants account for 5% of global emissions of carbon dioxide. Asglobal warming and ocean acidification become an increasing problem andthe desire to reduce carbon dioxide gas emissions (a principal cause ofglobal warming) continues, the cement production industry will fallunder increased scrutiny.

In addition to the pollution problems associated with Portland cementproduction, the durability of structures produced with Portland cementsis a major repair and maintenance expense, mainly because of theinstability of the cured product produced from Portland cement.

SUMMARY

Hydraulic cement compositions that include a carbonate compoundcomposition, e.g., a salt-water derived carbonate compound compositioncontaining crystalline and/or amorphous carbonate compounds, areprovided. Also provided are methods of making and using the hydrauliccements, as well as settable compositions, such as concretes andmortars, prepared therefrom. The cements and compositions producedtherefrom find use in a variety of applications, including use in avariety of building materials and building applications.

BRIEF DESCRIPTION OF THE FIGURES

FIG. 1 provides a flow diagram of a precipitation process according toan embodiment of the invention.

FIG. 2 provides a schematic of a system according to one embodiment ofthe invention.

FIG. 3 provides an XRD analysis of the P00099 precipitate reported inthe Experimental section, below.

FIG. 4 provides an FT-IR analysis of the P00099 precipitate reported inthe Experimental section, below.

FIGS. 5A and 5B provide SEM observations of the P00099 precipitatereported in the Experimental section, below.

FIG. 6 provides a visual representation of the particle sizedistribution of the P00099 precipitate.

FIGS. 7 and 8 provide results of strength attainment studies withblended cements according to embodiments of the invention.

FIG. 9 provides results of a shrinkage study with a blended cementaccording to an embodiment of the invention.

DETAILED DESCRIPTION

Hydraulic cement compositions that include a carbonate compoundcomposition, e.g., a salt-water derived carbonate compound compositioncontaining crystalline and/or amorphous carbonate compounds, areprovided. Also provided are methods of making and using the hydrauliccements, as well as settable compositions, such as concretes andmortars, prepared therefrom. The cements and compositions producedtherefrom find use in a variety of applications, including use in avariety of building materials and building applications.

Before the present invention is described in greater detail, it is to beunderstood that this invention is not limited to particular embodimentsdescribed, as such may, of course, vary. It is also to be understoodthat the terminology used herein is for the purpose of describingparticular embodiments only, and is not intended to be limiting, sincethe scope of the present invention will be limited only by the appendedclaims.

Where a range of values is provided, it is understood that eachintervening value, to the tenth of the unit of the lower limit unlessthe context clearly dictates otherwise, between the upper and lowerlimit of that range and any other stated or intervening value in thatstated range, is encompassed within the invention. The upper and lowerlimits of these smaller ranges may independently be included in thesmaller ranges and are also encompassed within the invention, subject toany specifically excluded limit in the stated range. Where the statedrange includes one or both of the limits, ranges excluding either orboth of those included limits are also included in the invention.

Certain ranges are presented herein with numerical values being precededby the term “about.” The term “about” is used herein to provide literalsupport for the exact number that it precedes, as well as a number thatis near to or approximately the number that the term precedes. Indetermining whether a number is near to or approximately a specificallyrecited number, the near or approximating unrecited number may be anumber which, in the context in which it is presented, provides thesubstantial equivalent of the specifically recited number.

Unless defined otherwise, all technical and scientific terms used hereinhave the same meaning as commonly understood by one of ordinary skill inthe art to which this invention belongs. Although any methods andmaterials similar or equivalent to those described herein can also beused in the practice or testing of the present invention, representativeillustrative methods and materials are now described.

All publications and patents cited in this specification are hereinincorporated by reference as if each individual publication or patentwere specifically and individually indicated to be incorporated byreference and are incorporated herein by reference to disclose anddescribe the methods and/or materials in connection with which thepublications are cited. The citation of any publication is for itsdisclosure prior to the filing date and should not be construed as anadmission that the present invention is not entitled to antedate suchpublication by virtue of prior invention. Further, the dates ofpublication provided may be different from the actual publication dateswhich may need to be independently confirmed.

It is noted that, as used herein and in the appended claims, thesingular forms “a,” “an,” and “the” include plural references unless thecontext clearly dictates otherwise. It is further noted that the claimsmay be drafted to exclude any optional element. As such, this statementis intended to serve as antecedent basis for use of such exclusiveterminology as “solely,” “only” and the like in connection with therecitation of claim elements, or use of a “negative” limitation.

As will be apparent to those of skill in the art upon reading thisdisclosure, each of the individual embodiments described and illustratedherein has discrete components and features which may be readilyseparated from or combined with the features of any of the other severalembodiments without departing from the scope or spirit of the presentinvention. Any recited method can be carried out in the order of eventsrecited or in any other order which is logically possible.

In further describing the subject invention, the hydraulic cementcompositions, as well as methods and systems for their production, willbe described first in greater detail. Next, concretes prepared from thehydraulic cements of the invention, as well as methods of using thesame, will be reviewed further.

Hydraulic Cement Comprising Carbonate Precipitate Component

Aspects of the invention include hydraulic cements. The term “hydrauliccement” is employed in its conventional sense to refer to a compositionwhich sets and hardens after combining with water or a solution wherethe solvent is water, e.g., an admixture solution. Setting and hardeningof the product produced by combination of the cements of the inventionwith an aqueous liquid results from the production of hydrates that areformed from the cement upon reaction with water, where the hydrates areessentially insoluble in water.

The hydraulic cement compositions are dry particulate compositions,e.g., powders. In certain embodiments, the dry particulate compositionsare made up of particles having an average particle size ranging from0.1 to 100 microns, such as 10 to 40 microns as determined using anyconvenient particle size determination protocol, such as Multi-detectorlaser scattering or sieving (i.e. <38 microns). In certain embodiments,multimodal, e.g., bimodal or other, distributions are present. Bimodaldistributions allow the surface area to be minimized, thus allowing alower liquids/solids mass ration for the cement yet providing smallerreactive particles for early reaction. In these instances, the averageparticle size of the larger size class can be upwards of 1000 microns (1mm). The surface area of the components making up the cement may vary. Agiven cement may have an average surface area sufficient to provide fora liquids to solids ratio upon combination with a liquid to produce asettable composition (e.g., as described in greater detail below)ranging from 0.5 m²/gm to 50 m²/gm, such as 0.75 to 20 m²/gm andincluding 0.80 to 10 m²/gm. In certain embodiments, the surface area ofthe cement ranges from 0.9 to 5 m²/gm, such as 0.95 to 2 m²/gm andincluding 1 to 2 m²/gm, as determined using the surface areadetermination protocol described in Breunner, Emmit and Teller 1953.

Hydraulic cements of the invention include a carbonate compoundcomposition. The carbonate compound compositions of the cements aremetastable carbonate compounds that are precipitated from a water, suchas an alkaline-earth-metal-containing water, e.g., a salt-water, asdescribed in greater detail below. The carbonate compound compositionsof the invention included precipitated crystalline and/or amorphouscarbonate compounds.

The water employed in the invention is analkaline-earth-metal-containing water. Accordingly, the water employedin the process is one that includes one or more alkaline earth metals,e.g., magnesium, calcium, etc. Waters of interest include those thatinclude calcium in amounts ranging from 50 to 20,000 ppm, such as 100 to10,0000 ppm and including 200 to 5000 ppm. Waters of interest includethose that include magnesium in amounts ranging from 50 to 20,000 ppm,such as 200 to 10000 ppm and including 500 to 5000 ppm.

In certain embodiments, the water from which the carbonate compoundcomposition is precipitated is a saltwater. In such embodiments, thecarbonate compound composition may be viewed as a saltwater derivedcarbonate compound composition. As used herein, “saltwater-derivedcarbonate compound composition” means a composition derived fromsaltwater and made up of one or more different carbonate crystallineand/or amorphous compounds with or without one or more hydroxidecrystalline or amorphous compounds. The term “saltwater” is employed inits conventional sense to refer to a number of different types ofaqueous liquids other than fresh water, where the term “saltwater”includes brackish water, sea water and brine (including man-made brines,e.g., geothermal plant wastewaters, desalination waste waters, etc), aswell as other salines having a salinity that is greater than that offreshwater. Brine is water saturated or nearly saturated with salt andhas a salinity that is 50 ppt (parts per thousand) or greater. Brackishwater is water that is saltier than fresh water, but not as salty asseawater, having a salinity ranging from 0.5 to 35 ppt. Seawater iswater from a sea or ocean and has a salinity ranging from 35 to 50 ppt.The saltwater source from which the mineral composition of the cementsof the invention is derived may be a naturally occurring source, such asa sea, ocean, lake, swamp, estuary, lagoon, etc., or a man-made source.In certain embodiments, the saltwater source of the mineral compositionis seawater.

While the present invention is described primarily in terms of saltwatersources, in certain embodiments, the water employed in the invention maybe a mineral rich, e.g., calcium and/or magnesium rich, freshwatersource.

The saltwater-derived mineral compositions of embodiments of embodimentsof the cements are ones that are derived from a saltwater. As such, theyare compositions that are obtained from a saltwater in some manner,e.g., by treating a volume of a saltwater in a manner sufficient toproduce the desired carbonate compound composition from the initialvolume of saltwater. In certain embodiments, the saltwater-derivedcarbonate compound compositions of the cements are derived fromsaltwater by precipitating them from the saltwater. In certainembodiments, the carbonate compound compositions are separated in solidform from a saltwater, as by means of a reagent, such as developed ingreater detail below.

The compounds of the hydraulic cements of the invention are ones whichinclude carbonate compounds and/or hydroxide compounds that, uponcombination with fresh water, dissolve and produce different compoundsthat are more stable in fresh water than compounds of thesaltwater-derived carbonate compound composition. The compounds of thecarbonate compositions may be ones that are more stable in salt waterthan they are in freshwater, such that they may be viewed as saltwatermetastable compounds.

The saltwater-derived carbonate compound compositions may include one ormore different carbonate compounds, such as two or more differentcarbonate compounds, e.g., three or more different carbonate compounds,five or more different carbonate compounds, etc., and may furtherinclude one or more, such as two or more, e.g., three or more, differenthydroxide compounds. The particular compound profile, i.e., the identityof the different types of different carbonate and/or hydroxide compoundsand the amounts of each, in a given carbonate compound composition mayvary and will be dependent on the particular nature of the water fromwhich it is derived, as well as the particular conditions employed toderive it.

As indicated above, the compounds of the carbonate compound compositionsare metastable carbonate compounds (and may include one or moremetastable hydroxide compounds) that are more stable in saltwater thanin freshwater, such that upon contact with fresh water of any pH theydissolve and re-precipitate into other fresh water stable compounds,e.g., minerals. The carbonate compounds may be amorphous or crystalline.In certain embodiments, the carbonate compounds are present as smallparticles, e.g., with crystal sizes ranging from 0.1 microns to 100microns, such as 0.5 to 10 microns, as determined by Scanning electronmicroscopy. In certain embodiments, the crystals have a high surfacearea, e.g., ranging from 0.5 to 50 m² sq./gm, such as from 0.5 to 2.0m²/gm, as determined by Brauner, Emmit, & Teller (BET) Surface AreaAnalysis.

The carbonate and hydroxide compounds of the cements may include anumber of different cations, such as but not limited to: calcium,magnesium, sodium, potassium, sulfur, boron, silicon, strontium, andcombinations thereof, where specific carbonate minerals of interestinclude, but are not limited to: calcium carbonate minerals, magnesiumcarbonate minerals and calcium magnesium carbonate minerals. Calciumcarbonate minerals of interest include, but are not limited to: calcite(CaCO₃), aragonite (CaCO₃), vaterite (CaCO₃), ikaite (CaCO₃.6H₂O), andamorphous calcium carbonate (CaCO₃.nH₂O). Magnesium carbonate mineralsof interest include, but are not limited to: magnesite (MgCO₃),barringtonite (MgCO₃.2H₂O), nesquehonite (MgCO₃.3H₂O), lanfordite(MgCO₃.5H₂O) and amorphous magnesium calcium carbonate (MgCO₃.nH₂O).Calcium magnesium carbonate minerals of interest include, but are notlimited to dolomite (CaMgCO₃), huntitte (CaMg(CO₃)₄) and sergeevite(Ca₂Mg₁₁(CO₃)₁₃.H₂O). The principal calcium hydroxide mineral ofinterest is portlandite (Ca(OH)₂), and amorphous hydrated analogsthereof. The principal magnesium hydroxide mineral of interest isbrucite (Mg(OH)₂), and amorphous hydrated analogs thereof.

As the carbonate compound compositions of embodiments of the inventionare derived from a salt water source, they will include one or morecomponents that are present in the salt water source and identify thecompound compositions that come from the salt water source, where theseidentifying components and the amounts thereof are collectively referredto herein as a saltwater source identifier. For example, if thesaltwater source is sea water, identifying that may be present in thecarbonate and hydroxide mineral composition include, but are not limitedto: chloride, sodium, sulfur, potassium, bromide, silicon, strontium andthe like. Any such source-identifying or “marker” elements are generallypresent in small amounts, e.g., in amounts of 20,000 ppm or less, suchas amounts of 2000 ppm or less. In certain embodiments, the “marker”compound is strontium, which may be present in the precipitatedincorporated into the aragonite lattice, and make up 10,000 ppm or less,ranging in certain embodiments from 3 to 10,000 ppm, such as from 5 to5000 ppm, including 5 to 1000 ppm, e.g., 5 to 500 ppm, including 5 to100 ppm. Another “marker” compound of interest is magnesium, which maybe present in amounts of up to 20% mole substitution for calcium incarbonate compounds. The saltwater source identifier of the compositionsmay vary depending on the particular saltwater source employed toproduce the saltwater-derived carbonate composition. In certainembodiments, the calcium carbonate content of the cement is 25% w/w orhigher, such as 40% w/w or higher, and including 50% w/w or higher,e.g., 60% w/w. The carbonate compound composition has, in certainembodiments, a calcium/magnesium ratio that is influenced by, andtherefore reflects, the water source from which it has beenprecipitated. In certain embodiments, the calcium/magnesium molar ratioranges from 10/1 to 1/5 Ca/Mg, such as 5/1 to 1/3 Ca/Mg. In certainembodiments, the carbonate composition is characterized by having anwater source identifying carbonate to hydroxide compound ratio, where incertain embodiments this ratio ranges from 100 to 1, such as 10 to 1 andincluding 1 to 1.

The proportion of the cement that is the precipitated carbonate compoundcomposition may vary. In certain embodiments, the cement includes from 5to 50% w/w, such as 5 to 25% w/w including 5 to 10% w/w of carbonatecompound composition. In certain embodiments, the carbonate compoundcomposition makes up greater than 50% of the cement. In certainembodiments, the cement includes from 25 to 80% w/w, such as 50 to 75%w/w including 75 to 80% w/w of carbonate compound composition. Incertain embodiments, the carbonate compound composition makes up greaterthan 80% w/w or more of the cement, e.g., 90% w/w or more of the cement.The cement may be entirely made up of the saltwater derived carbonatecompound composition, or include one or more additional components.

In certain embodiments, the cements are blends, in that they include notonly the carbonate compound composition component but also one or moreadditional components that are added to modify the properties of thecement, e.g., to provide desired strength attainment, to provide desiredsetting times, etc. Components of interest that may be present inblended cements of the invention include, but are not limited to: blastfurnace slag, fly ash, diatomaceous earth, and other natural orartificial pozzolans, silica fumes, limestone, gypsum, hydrated lime,air entrainers, retarders, waterproofers and coloring agents. The amountof such components present in a given blended cement of the inventionmay vary, and in certain embodiments the amounts of these componentsrange from 1 to 50% w/w, such as 2 to 10% w/w.

Of interest in certain embodiments are Portland cement blends. Thephrase “Portland cement blend” refers to a hydrualic cement compositionthat includes a Portland cement component and significant amount of anon-Portland cement component. As the cements of the invention arePortland cement blends, the cements include a Portland cement component.The Portland cement component may be any convenient Portland cement. Asis known in the art, Portland cements are powder compositions producedby grinding Portland cement clinker (more than 90%), a limited amount ofcalcium sulfate which controls the set time, and up to 5% minorconstituents (as allowed by various standards). As defined by theEuropean Standard EN197.1, “Portland cement clinker is a hydraulicmaterial which shall consist of at least two-thirds by mass of calciumsilicates (3CaO.SiO₂ and 2CaO.SiO₂), the remainder consisting ofaluminium- and iron-containing clinker phases and other compounds. Theratio of CaO to SiO₂ shall not be less than 2.0. The magnesium content(MgO) shall not exceed 5.0% by mass.” In certain embodiments, thePortland cement constituent of the present invention is any Portlandcement that satisfies the ASTM Standards and Specifications of C150(Types I-VIII) of the American Society for Testing of Materials (ASTMC50-Standard Specification for Portland Cement). ASTM C150 covers eighttypes of portland cement, each possessing different properties, and usedspecifically for those properties.

In a given Portland cement blend composition of the invention, theamount of Portland cement component may vary. In certain embodiments,the amount of Portland cement in the blend ranges from 10 to 90% (w/w),such as 30 to 70% (w/w) and including 40 to 60% (w/w), e.g., a blend of80% OPC and 20% carbonate compound cement of the invention.

In certain embodiments, the cements further include a pH regulatingagent which influences the pH of the fluid component of settablecomposition produced from the cement (e.g., a mortar or concrete) uponcombination of the cement with water. Of interest are agents thatprovide for an alkaline environment upon combination with water, e.g.,where the pH of the hydrated cement is 12 or higher, such as 13 orhigher, and including 13.5 or higher. In certain embodiments, the pHregulating (i.e., modulating) agent is an oxide or hydroxide, e.g.,calcium oxide, calcium hydroxide, magnesium oxide or magnesiumhydroxide. When present, such agents may be present in amounts rangingfrom 1 to 10% w/w, such as 2 to 5% w/w.

In certain embodiments, the cement includes an amount of aggregate.Aggregate can be included in the cementitious composition to provide formortars which include fine aggregate, and concretes which also includecoarse aggregate. The fine aggregates are materials that almost entirelypass through a Number 4 sieve (ASTM C 125 and ASTM C 33), such as silicasand. The coarse aggregate are materials that are predominantly retainedon a Number 4 sieve (ASTM C 125 and ASTM C 33), such as silica, quartz,crushed round marble, glass spheres, granite, limestone, calcite,feldspar, alluvial sands, sands or any other durable aggregate, andmixtures thereof. As such, the term “aggregate” is used broadly to referto a number of different types of both coarse and fine particulatematerial, including but not limited to: sand, gravel, crushed stone,slag, and recycled concrete. The amount and nature of the aggregate mayvary widely. In certain embodiments, the amount of aggregate may rangefrom 25 to 80%, such as 40 to 70% and including 50 to 70% w/w of thetotal composition made up of both the cement component and theaggregate.

Specific hydraulic cement formulations of interest are described ingreater detail in the Experimental Section, below.

Production of Saltwater-Derived Mineral Component

As reviewed above, the hydraulic cements are cements that include acarbonate compound composition, such as a saltwater-derived carbonatecompound composition. As such, the carbonate compound composition of thecements is one that is made up of one or more different carbonatecompounds, which may be amorphous or crystalline. As reviewed above, thecarbonate compound compositions of the cements may include one or morehydroxide compounds.

As reviewed above, the carbonate compounds compositions are produced byprecipitation from an alkaline-earth-metal-containing water, e.g., asaltwater. The saltwater employed in methods may vary. As reviewedabove, saltwaters of interest include brackish water, sea water andbrine, as well as other salines having a salinity that is greater thanthat of freshwater (which has a salinity of less than 5 ppt dissolvedsalts).

In methods of producing the carbonate compound compositions of thecements of the invention, a volume of water is subjected to carbonatecompound precipitation conditions sufficient to produce a precipitatedcarbonate compound composition and a mother liquor (i.e., the part ofthe water that is left over after precipitation of the carbonatecompound(s) from the saltwater). Any convenient precipitation conditionsmay be employed, which conditions result in the production of acarbonate compound composition.

Precipitation conditions of interest may vary. For example, thetemperature of the water may be within a suitable range for theprecipitation of the desired mineral to occur. In some embodiments, thetemperature of the water may be in a range from 5 to 70° C., such asfrom 20 to 50° C. and including from 25 to 45° C. As such, while a givenset of precipitation conditions may have a temperature ranging from 0 to100° C., the temperature of the water may have to be adjusted in certainembodiments to produce the desired precipitate.

In normal sea water 93% of the dissolved CO₂ is in the form ofbicarbonate ions (HCO₃ ⁻) and 6% is in the form of carbonate ions (CO₃⁻²). When calcium carbonate precipitates from normal sea water, CO₂ isreleased. Above pH 10.33, greater than 90% of the carbonate is in theform of carbonate ion, and no CO₂ is released during the precipitationof calcium carbonate. While the pH of the water employed in methods mayrange from 5 to 14 during a given precipitation process, in certainembodiments the pH is raised to alkaline levels in order to drive theprecipitation of carbonate compounds, as well as other compounds, e.g.,hydroxide compounds, as desired. In certain of these embodiments, the pHis raised to a level which minimizes if not eliminates CO₂ productionduring precipitation, causing dissolved CO₂, e.g., in the form ofcarbonate and bicarbonate, to be trapped in the carbonate compoundprecipitate. In these embodiments, the pH may be raised to 10 or higher,such as 11 or higher.

The pH of the water may be raised using any convenient approach. Incertain embodiments, a pH raising agent may be employed, where examplesof such agents include oxides, hydroxides (e.g., potassium hydroxide,sodium hydroxide, brucite (Mg(OH₂), etc.), carbonates (e.g. sodiumcarbonate) and the like. One such approach would be to use the coal ashfrom a coal-fired power plant, which contains many oxides, to elevatethe pH of sea water. Other coal processes, like the gasification ofcoal, to produce syngas, also produce hydrogen gas and carbon monoxide,and may serve as a source of hydroxide as well, Some naturally occurringminerals, such as serpintine, contain hydroxide, and can be dissolved,yielding a hydroxide source. The amount of pH elevating agent that isadded to the water will depend on the particular nature of the agent andthe volume of saltwater being modified, and will be sufficient to raisethe pH of the water to the desired value. Alternatively, the pH of thesaltwater source can be raised to the desired level by electrolysis ofthe water. Where electrolysis is employed, a variety of differentprotocols may be taken, such as use of the Mercury cell process (alsocalled the Castner-Kellner process); the Diaphragm cell process and themembrane cell process. Where desired, byproducts of the hydrolysisproduct, e.g., H₂, sodium metal, etc. may be harvested and employed forother purposes, as desired.

Additives other than pH elevating agents may also be introduced into thewater in order to influence the nature of the precipitate that isproduced. As such, certain embodiments of the methods include providingan additive in water before or during the time when the water issubjected to the precipitation conditions. Certain calcium carbonatepolymorphs can be favored by trace amounts of certain additives. Forexample, vaterite, a highly unstable polymorph of CaCO₃ whichprecipitates in a variety of different morphologies and converts rapidlyto calcite, can be obtained at very high yields by including traceamounts of lanthanum as lanthanum chloride in a supersaturated solutionof calcium carbonate. Other additives beside lathanum that are ofinterest include, but are not limited to transition metals and the like.For instance, iron is known to favor the formation of disordereddolomite (protodolomite) where it would not form otherwise.

The nature of the precipitate can also be influenced by selection ofappropriate major ion ratios. Major ion ratios also have considerableinfluence of polymorph formation. For example, as the magnesium:calciumratio in the water increases, aragonite becomes the favored polymorph ofcalcium carbonate over low-magnesium calcite. At low magnesium:calciumratios, low-magnesium calcite is the preferred polymorph.

Rate of precipitation also impacts compound phase formation and may becontrolled in a manner sufficient to produce a desired precipitateproduct. The most rapid precipitation can be achieved by seeding thesolution with a desired phase. Without seeding, rapid precipitation canbe achieved by rapidly increasing the pH of the sea water, which resultsin more amorphous constituents. The higher the pH is, the more rapid theprecipitation is and the more amorphous the precipitate is.

Accordingly, a set of precipitation conditions to produce a desiredprecipitate from a water include, in certain embodiments, the water'stemperature and pH, and in some instances the concentrations ofadditives and ionic species in the water. Precipitation conditions mayalso include factors such as mixing rate, forms of agitation such asultrasonics, and the presence of seed crystals, catalysts, membranes, orsubstrates. In some embodiments, precipitation conditions includesupersaturated conditions, temperature, pH, and/or concentrationgradients, or cycling or changing any of these parameters. The protocolsemployed to prepare carbonate compound precipitates according to theinvention may be batch or continuous protocols. It will be appreciatedthat precipitation conditions may be different to produce a givenprecipitate in a continuous flow system compared to a batch system.

In certain embodiments, the methods further include contacting thevolume of water that is subjected to the mineral precipitationconditions with a source of CO₂. Contact of the water with the sourceCO₂ may occur before and/or during the time when the water is subject toCO₂ precipitation conditions. Accordingly, embodiments of the inventioninclude methods in which the volume of water is contacted with a sourceof CO₂ prior to subjecting the volume of saltwater to mineralprecipitation conditions. Embodiments of the invention include methodsin which the volume of salt water is contacted with a source of CO₂while the volume of saltwater is being subjected to mineralprecipitation conditions. Embodiments of the invention include methodsin which the volume of water is contacted with a source of a CO₂ bothprior to subjecting the volume of water to mineral precipitationconditions and while the volume of water is being subjected to carbonatecompound precipitation conditions.

The source of CO₂ that is contacted with the volume of water in theseembodiments may be any convenient CO₂ source. The CO₂ source may be aliquid, solid (e.g., dry ice) or gaseous CO₂ source. In certainembodiments, the CO₂ source is a gaseous CO₂ source. This gaseous CO₂is, in certain instances, a waste stream or product from an industrialplant. The nature of the industrial plant may vary in these embodiments,where industrial plants of interest include power plants, chemicalprocessing plants, and other industrial plants that produce CO₂ as abyproduct. By waste stream is meant a stream of gas (or analogousstream) that is produced as a byproduct of an active process of theindustrial plant. The gaseous stream may be substantially pure CO₂ or amuticomponent gaseous stream that includes CO₂ and one or moreadditional gases. Multicomponent gaseous streams (containing CO₂) thatmay be employed as a CO₂ source in embodiments of the subject methodsinclude both reducing, e.g., syngas, shifted syngas, natural gas, andhydrogen and the like, and oxidizing condition streams, e.g., flue gasesfrom combustion. Particular multicomponent gaseous streams of interestthat may be treated according to the subject invention include: oxygencontaining combustion power plant flue gas, turbo charged boiler productgas, coal gasification product gas, shifted coal gasification productgas, anaerobic digester product gas, wellhead natural gas stream,reformed natural gas or methane hydrates, and the like.

The volume of water may be contacted with the CO₂ source using anyconvenient protocol. Where the CO₂ is a gas, contact protocols ofinterest include, but are not limited to: direct contacting protocols,e.g., bubbling the gas through the volume of saltwater, concurrentcontacting means, i.e., contact between unidirectionally flowing gaseousand liquid phase streams, countercurrent means, i.e., contact betweenoppositely flowing gaseous and liquid phase streams, and the like. Thus,contact may be accomplished through use of infusers, bubblers, fluidicVenturi reactor, sparger, gas filter, spray, tray, or packed columnreactors, and the like, as may be convenient.

Following production of the carbonate compound precipitate from thewater, the resultant precipitated carbonate compound composition isseparated from the mother liquor to produce separated carbonate compoundprecipitate product. Separation of the precipitate can be achieved usingany convenient approach, including a mechanical approach, e.g., wherebulk excess water is drained from the precipitated, e.g., either bygravity alone or with the addition of vacuum, mechanical pressing, byfiltering the precipitate from the mother liquor to produce a filtrate,etc. Separation of bulk water produces a wet, dewatered precipitate.

The resultant dewatered precipitate is then dried to produce a product.Drying can be achieved by air drying the filtrate. Where the filtrate isair dried, air drying may be at a temperature ranging from −70 to 120°C., as desired. In certain embodiments, drying is achieved byfreeze-drying (i.e., lyophilization), where the precipitate is frozen,the surrounding pressure is reduced and enough heat is added to allowthe frozen water in the material to sublime directly from the frozenprecipitate phase to gas. In yet another embodiment, the precipitate isspray dried to dry the precipitate, where the liquid containing theprecipitate is dried by feeding it through a hot gas (such as thegaseous waste stream from the power plant), e.g., where the liquid feedis pumped through an atomizer into a main drying chamber and a hot gasis passed as a co-current or counter-current to the atomizer direction.Depending on the particular drying protocol of the system, the dryingstation may include a filtration element, freeze drying structure, spraydrying structure, etc.

Where desired, the precipitate may be stored in the mother liquor for aperiod of time following precipitation and prior to separation, e.g., bydrying. For example, the precipitate may be stored in the mother liquorfor a period of time ranging from 1 to 1000 days or longer, such as 1 to10 days or longer, at a temperature ranging from 1 to 40° C., such as 20to 25° C.

FIG. 1 provides a schematic flow diagram of a carbonate precipitationprocess according to an embodiment of the invention. In FIG. 1,saltwater from salt water source 10 is subjected to carbonate compoundprecipitation conditions at precipitation step 20. As reviewed above,term “saltwater” is employed in its conventional sense to refer a numberof different types of aqueous fluids other than fresh water, where theterm “saltwater” includes brackish water, sea water and brine (includingman-made brines, e.g., geothermal plant wastewaters, desalination wastewaters, etc), as well as other salines having a salinity that is greaterthan that of freshwater. The saltwater source from which the carbonatecompound composition of the cements of the invention is derived may be anaturally occurring source, such as a sea, ocean, lake, swamp, estuary,lagoon, etc., or a man-made source.

In certain embodiments, the water may be obtained from the power plantthat is also providing the gaseous waste stream. For example, in watercooled power plants, such as seawater cooled power plants, water thathas been employed by the power plant may then be sent to theprecipitation system and employed as the water in the precipitationreaction. In certain of these embodiments, the water may be cooled priorto entering the precipitation reactor.

In the embodiment depicted in FIG. 1, the water from saltwater source 10is first charged with CO₂ to produce CO₂ charged water, which CO₂ isthen subjected to carbonate compound precipitation conditions. Asdepicted in FIG. 1, a CO₂ gaseous stream 30 is contacted with the waterat precipitation step 20. The provided gaseous stream 30 is contactedwith a suitable water at precipitation step 20 to produce a CO₂ chargedwater. By CO₂ charged water is meant water that has had CO₂ gascontacted with it, where CO₂ molecules have combined with watermolecules to produce, e.g., carbonic acid, bicarbonate and carbonateion. Charging water in this step results in an increase in the “CO₂content” of the water, e.g., in the form of carbonic acid, bicarbonateand carbonate ion, and a concomitant decrease in the pCO₂ of the wastestream that is contacted with the water. The CO₂ charged water isacidic, having a pH of 6 or less, such as 5 or less and including 4 orless. In certain embodiments, the concentration of CO₂ of the gas thatis used to charge the water is 10% or higher, 25% or higher, including50% or higher, such as 75% or even higher. Contact protocols of interestinclude, but are not limited to: direct contacting protocols, e.g.,bubbling the gas through the volume of water, concurrent contactingmeans, i.e., contact between unidirectionally flowing gaseous and liquidphase streams, countercurrent means, i.e., contact between oppositelyflowing gaseous and liquid phase streams, and the like. Thus, contactmay be accomplished through use of infusers, bubblers, fluidic Venturireactor, sparger, gas filter, spray, tray, or packed column reactors,and the like, as may be convenient.

At precipitation step 20, carbonate compounds, which may be amorphous orcrystalline, are precipitated. Precipitation conditions of interestinclude those that change the physical environment of the water toproduce the desired precipitate product. For example, the temperature ofthe water may be raised to an amount suitable for precipitation of thedesired carbonate compound(s) to occur. In such embodiments, thetemperature of the water may be raised to a value from 5 to 70° C., suchas from 20 to 50° C. and including from 25 to 45° C. As such, while agiven set of precipitation conditions may have a temperature rangingfrom 0 to 100° C., the temperature may be raised in certain embodimentsto produce the desired precipitate. In certain embodiments, thetemperature is raised using energy generated from low or zero carbondioxide emission sources, e.g., solar energy source, wind energy source,hydroelectric energy source, etc. While the pH of the water may rangefrom 7 to 14 during a given precipitation process, in certainembodiments the pH is raised to alkaline levels in order to drive theprecipitation of carbonate compound as desired. In certain of theseembodiments, the pH is raised to a level which minimizes if noteliminates CO₂ gas generation production during precipitation. In theseembodiments, the pH may be raised to 10 or higher, such as 11 or higher.Where desired, the pH of the water is raised using any convenientapproach. In certain embodiments, a pH raising agent may be employed,where examples of such agents include oxides, hydroxides (e.g., sodiumhydroxide, potassium hydroxide, brucite), carbonates (e.g. sodiumcarbonate) and the like. The amount of pH elevating agent that is addedto the saltwater source will depend on the particular nature of theagent and the volume of saltwater being modified, and will be sufficientto raise the pH of the salt water source to the desired value.Alternatively, the pH of the saltwater source can be raised to thedesired level by electrolysis of the water.

CO₂ charging and carbonate compound precipitation may occur in acontinuous process or at separate steps. As such, charging andprecipitation may occur in the same reactor of a system, e.g., asillustrated in FIG. 1 at step 20, according to certain embodiments ofthe invention. In yet other embodiments of the invention, these twosteps may occur in separate reactors, such that the water is firstcharged with CO₂ in a charging reactor and the resultant CO₂ chargedwater is then subjected to precipitation conditions in a separatereactor.

Following production of the carbonate precipitate from the water, theresultant precipitated carbonate compound composition is separated fromthe mother liquor to produce separated carbonate compound precipitateproduct, as illustrated at step 40 of FIG. 1. Separation of theprecipitate can be achieved using any convenient approach, including amechanical approach, e.g., where bulk excess water is drained from theprecipitated, e.g., either by gravity alone or with the addition ofvacuum, mechanical pressing, by filtering the precipitate from themother liquor to produce a filtrate, etc. Separation of bulk waterproduces a wet, dewatered precipitate.

The resultant dewatered precipitate is then dried to produce a product,as illustrated at step 60 of FIG. 1. Drying can be achieved by airdrying the filtrate. Where the filtrate is air dried, air drying may beat room or elevated temperature. In yet another embodiment, theprecipitate is spray dried to dry the precipitate, where the liquidcontaining the precipitate is dried by feeding it through a hot gas(such as the gaseous waste stream from the power plant), e.g., where theliquid feed is pumped through an atomizer into a main drying chamber anda hot gas is passed as a co-current or counter-current to the atomizerdirection. Depending on the particular drying protocol of the system,the drying station may include a filtration element, freeze dryingstructure, spray drying structure, etc.

Where desired, the dewatered precipitate product from the separationreactor 40 may be washed before drying, as illustrated at optional step50 of FIG. 1. The precipitate may be washed with freshwater, e.g., toremove salts (such as NaCl) from the dewatered precipitate. Used washwater may be disposed of as convenient, e.g., by disposing of it in atailings pond, etc.

At step 70, the dried precipitate is refined, e.g., to provide fordesired physical characteristics, such as particle size, surface area,etc., or to add one or more components to the precipitate, such asadmixtures, aggregate, supplementary cementitious materials, etc., toproduce a final product 80.

In certain embodiments, a system is employed to perform the abovemethods, where such systems include those described below in greaterdetail.

Settable Compositions

Additional aspects of the invention are settable compositions, e.g.,pure cements, concretes and mortars, which include a hydraulic cement ofthe invention that includes a carbonate compound composition component,such as a saltwater derived carbonate compound component, e.g., asdescribed above, aggregate and an aqueous fluid, e.g., water. Settablecompositions of the invention, such as concretes and mortars, areproduced by combining the cement with an amount of aggregate (fine formortar, e.g., sand; coarse with or without fine for concrete) and water,either at the same time or by pre-combining the cement with aggregate,and then combining the resultant dry components with water. The choiceof coarse aggregate material for concrete mixes using cementcompositions of the invention may have a minimum size of about ⅜ inchand can vary in size from that minimum up to one inch or larger,including in gradations between these limits. Crushed limestone andother rocks, gravel and the like are coarse aggregates of interest.Finely divided aggregate is smaller than ⅜ inch in size and again may begraduated in much finer sizes down to 200-sieve size or so. Groundlimestone and other rocks, sand and the like are fine aggregates ofinterest. Fine aggregates may be present in both mortars and concretesof the invention. The weight ratio of cement to aggregate in the drycomponents of the cement may vary, and in certain embodiments rangesfrom 1:10 to 4:10, such as 2:10 to 5:10 and including from 55:1000 to70:100.

The liquid phase, e.g., aqueous fluid, with which the dry component iscombined to produce the settable composition, e.g., concrete, may vary,from pure water to water that includes one or more solutes, additives,co-solvents, etc., as desired. The ratio of dry component to liquidphase that is combined in preparing the settable composition may vary,and in certain embodiments ranges from 2:10 to 7:10, such as 3:10 to6:10 and including 4:10 to 6:10.

In certain embodiments, the cements may be employed with one or moreadmixtures. Admixtures are compositions added to concrete to provide itwith desirable characteristics that are not obtainable with basicconcrete mixtures or to modify properties of the concrete to make itmore readily useable or more suitable for a particular purpose or forcost reduction. As is known in the art, an admixture is any material orcomposition, other than the hydraulic cement, aggregate and water, thatis used as a component of the concrete or mortar to enhance somecharacteristic, or lower the cost, thereof. The amount of admixture thatis employed may vary depending on the nature of the admixture. Incertain embodiments the amounts of these components range from 1 to 50%w/w, such as 2 to 10% w/w.

Major reasons for using admixtures are: (1) to achieve certainstructural improvements in the resulting cured concrete; (2) to improvethe quality of concrete through the successive stages of mixing,transporting, placing, and curing during adverse weather or trafficconditions; (3) to overcome certain emergencies during concretingoperations; and (4) to reduce the cost of concrete construction. In someinstances, the desired concrete performance characteristics can only beachieved by the use of an admixture. In some cases, using an admixtureallows for the use of less expensive construction methods or designs,the savings from which can more than offset the cost of the admixture.

Admixtures of interest include finely divided mineral admixtures. Finelydivided mineral admixtures are materials in powder or pulverized formadded to concrete before or during the mixing process to improve orchange some of the plastic or hardened properties of Portland cementconcrete. The finely divided mineral admixtures can be classifiedaccording to their chemical or physical properties as: cementitiousmaterials; pozzolans; pozzolanic and cementitious materials; andnominally inert materials. A pozzolan is a siliceous or aluminosiliceousmaterial that possesses little or no cementitious value but will, in thepresence of water and in finely divided form, chemically react with thecalcium hydroxide released by the hydration of Portland cement to formmaterials with cementitious properties. Pozzolans can also be used toreduce the rate at which water under pressure is transferred throughconcrete. Diatomaceous earth, opaline cherts, clays, shales, fly ash,silica fume, volcanic tuffs and pumicites are some of the knownpozzolans. Certain ground granulated blast-furnace slags and highcalcium fly ashes possess both pozzolanic and cementitious properties.Nominally inert materials can also include finely divided raw quartz,dolomites, limestone, marble, granite, and others. Fly ash is defined inASTM C618.

One type of admixture of interest is a plasticizer. Plasticizers can beadded to a concrete to provide it with improved workability for ease ofplacement with reduced consolidating effort and in reinforced concretesthat are required to flow uniformly without leaving void space underreinforcing bars. Also of interest as admixtures are accelerators,retarders, air-entrainers, foaming agents, water reducers, corrosioninhibitors, and pigments. Accelerators are used to increase the curerate (hydration) of the concrete formulation and are of particularimportance in applications where it is desirable for the concrete toharden quickly and in low temperature applications. Retarders act toslow the rate of hydration and increase the time available to pour theconcrete and to form it into a desired shape. Retarders are ofparticular importance in applications where the concrete is being usedin hot climates. Air-entrainers are used to distribute tiny air bubblesthroughout the concrete. Air-entrainers are of particular value forutilization in regions that experience cold weather because the tinyentrained air bubbles help to allow for some contraction and expansionto protect the concrete from freeze-thaw damage. Pigments can also beadded to concrete to provide it with desired color characteristics foraesthetic purposes.

As such, admixtures of interest include, but are not limited to: setaccelerators, set retarders, air-entraining agents, defoamers,alkali-reactivity reducers, bonding admixtures, dispersants, coloringadmixtures, corrosion inhibitors, dampproofing admixtures, gas formers,permeability reducers, pumping aids, shrinkage compensation admixtures,fungicidal admixtures, germicidal admixtures, insecticidal admixtures,rheology modifying agents, finely divided mineral admixtures, pozzolans,aggregates, wetting agents, strength enhancing agents, water repellents,and any other concrete or mortar admixture or additive. When using anadmixture, the fresh cementitious composition, to which the admixtureraw materials are introduced, is mixed for sufficient time to cause theadmixture raw materials to be dispersed relatively uniformly throughoutthe fresh concrete.

Set accelerators are used to accelerate the setting and early strengthdevelopment of concrete. A set accelerator that can be used with theadmixture system can be, but is not limited to, a nitrate salt of analkali metal, alkaline earth metal, or aluminum; a nitrite salt of analkali metal, alkaline earth metal, or aluminum; a thiocyanate of analkali metal, alkaline earth metal or aluminum; an alkanolamine; athiosulfate of an alkali metal, alkaline earth metal, or aluminum; ahydroxide of an alkali metal, alkaline earth metal, or aluminum; acarboxylic acid salt of an alkali metal, alkaline earth metal, oraluminum (preferably calcium formate); a polyhydroxylalkylamine; ahalide salt of an alkali metal or alkaline earth metal (e.g., chloride).Examples of set accelerators that may be used in the present dispensingmethod include, but are not limited to, POZZOLITH®NC534, nonchloridetype set accelerator and/or RHEOCRETE®CNI calcium nitrite-basedcorrosion inhibitor, both sold under the above trademarks by BASFAdmixtures Inc. of Cleveland, Ohio.

Also of interest are set retarding admixtures. Set retarding, also knownas delayed-setting or hydration control, admixtures are used to retard,delay, or slow the rate of setting of concrete. They can be added to theconcrete mix upon initial batching or sometime after the hydrationprocess has begun. Set retarders are used to offset the acceleratingeffect of hot weather on the setting of concrete, or delay the initialset of concrete or grout when difficult conditions of placement occur,or problems of delivery to the job site, or to allow time for specialfinishing processes. Most set retarders also act as low level waterreducers and can also be used to entrain some air into concrete.Retarders that can be used include, but are not limited to an oxy-boroncompound, corn syrup, lignin, a polyphosphonic acid, a carboxylic acid,a hydroxycarboxylic acid, polycarboxylic acid, hydroxylated carboxylicacid, such as fumaric, itaconic, malonic, borax, gluconic, and tartaricacid, lignosulfonates, ascorbic acid, isoascorbic acid, sulphonicacid-acrylic acid copolymer, and their corresponding salts,polyhydroxysilane, polyacrylamide, carbohydrates and mixtures thereof.Illustrative examples of retarders are set forth in U.S. Pat. Nos.5,427,617 and 5,203,919, incorporated herein by reference. A furtherexample of a retarder suitable for use in the admixture system is ahydration control admixture sold under the trademark DELVO® by BASFAdmixtures Inc. of Cleveland, Ohio.

Also of interest as admixtures are air entrainers. The term airentrainer includes any substance that will entrain air in cementitiouscompositions. Some air entrainers can also reduce the surface tension ofa composition at low concentration. Air-entraining admixtures are usedto purposely entrain microscopic air bubbles into concrete.Air-entrainment dramatically improves the durability of concrete exposedto moisture during cycles of freezing and thawing. In addition,entrained air greatly improves concrete's resistance to surface scalingcaused by chemical deicers. Air entrainment also increases theworkability of fresh concrete while eliminating or reducing segregationand bleeding. Materials used to achieve these desired effects can beselected from wood resin, natural resin, synthetic resin, sulfonatedlignin, petroleum acids, proteinaceous material, fatty acids, resinousacids, alkylbenzene sulfonates, sulfonated hydrocarbons, vinsol resin,anionic surfactants, cationic surfactants, nonionic surfactants, naturalrosin, synthetic rosin, an inorganic air entrainer, syntheticdetergents, and their corresponding salts, and mixtures thereof. Airentrainers are added in an amount to yield a desired level of air in acementitious composition. Examples of air entrainers that can beutilized in the admixture system include, but are not limited to MB AE90, MB VR and MICRO AIR®, all available from BASF Admixtures Inc. ofCleveland, Ohio.

Also of interest as admixtures are defoamers. Defoamers are used todecrease the air content in the cementitious composition. Examples ofdefoamers that can be utilized in the cementitious composition include,but are not limited to mineral oils, vegetable oils, fatty acids, fattyacid esters, hydroxyl functional compounds, amides, phosphoric esters,metal soaps, silicones, polymers containing propylene oxide moieties,hydrocarbons, alkoxylated hydrocarbons, alkoxylated polyalkylene oxides,tributyl phosphates, dibutyl phthalates, octyl alcohols, water-insolubleesters of carbonic and boric acid, acetylenic diols, ethyleneoxide-propylene oxide block copolymers and silicones.

Also of interest as admixtures are dispersants. The term dispersant asused throughout this specification includes, among others,polycarboxylate dispersants, with or without polyether units. The termdispersant is also meant to include those chemicals that also functionas a plasticizer, water reducer such as a high range water reducer,fluidizer, antiflocculating agent, or superplasticizer for cementitiouscompositions, such as lignosulfonates, salts of sulfonated naphthalenesulfonate condensates, salts of sulfonated melamine sulfonatecondensates, beta naphthalene sulfonates, sulfonated melamineformaldehyde condensates, naphthalene sulfonate formaldehyde condensateresins for example LOMAR D® dispersant (Cognis Inc., Cincinnati, Ohio),polyaspartates, or oligomeric dispersants. Polycarboxylate dispersantscan be used, by which is meant a dispersant having a carbon backbonewith pendant side chains, wherein at least a portion of the side chainsare attached to the backbone through a carboxyl group or an ether group.Examples of polycarboxylate dispersants can be found in U.S. Pub. No.2002/0019459 A1, U.S. Pat. No. 6,267,814, U.S. Pat. No. 6,290,770, U.S.Pat. No. 6,310,143, U.S. Pat. No. 6,187,841, U.S. Pat. No. 5,158,996,U.S. Pat. No. 6,008,275, U.S. Pat. No. 6,136,950, U.S. Pat. No.6,284,867, U.S. Pat. No. 5,609,681, U.S. Pat. No. 5,494,516; U.S. Pat.No. 5,674,929, U.S. Pat. No. 5,660,626, U.S. Pat. No. 5,668,195, U.S.Pat. No. 5,661,206, U.S. Pat. No. 5,358,566, U.S. Pat. No. 5,162,402,U.S. Pat. No. 5,798,425, U.S. Pat. No. 5,612,396, U.S. Pat. No.6,063,184, U.S. Pat. No. 5,912,284, U.S. Pat. No. 5,840,114, U.S. Pat.No. 5,753,744, U.S. Pat. No. 5,728,207, U.S. Pat. No. 5,725,657, U.S.Pat. No. 5,703,174, U.S. Pat. No. 5,665,158, U.S. Pat. No. 5,643,978,U.S. Pat. No. 5,633,298, U.S. Pat. No. 5,583,183, and U.S. Pat. No.5,393,343, which are all incorporated herein by reference as if fullywritten out below. The polycarboxylate dispersants of interest includebut are not limited to dispersants or water reducers sold under thetrademarks GLENIUM® 3030NS, GLENIUM® 3200 HES, GLENIUM 3000NS® (BASFAdmixtures Inc., Cleveland, Ohio), ADVA® (W. R. Grace Inc., Cambridge,Mass.), VISCOCRETE® (Sika, Zurich, Switzerland), and SUPERFLUX® (AximConcrete Technologies Inc., Middlebranch, Ohio).

Also of interest as admixtures are alkali reactivity reducers. Alkalireactivity reducers can reduce the alkali-aggregate reaction and limitthe disruptive expansion forces that this reaction can produce inhardened concrete. The alkali-reactivity reducers include pozzolans (flyash, silica fume), blast-furnace slag, salts of lithium and barium, andother air-entraining agents.

Natural and synthetic admixtures are used to color concrete foraesthetic and safety reasons. These coloring admixtures are usuallycomposed of pigments and include carbon black, iron oxide,phthalocyanine, umber, chromium oxide, titanium oxide, cobalt blue, andorganic coloring agents.

Also of interest as admixtures are corrosion inhibitors. Corrosioninhibitors in concrete serve to protect embedded reinforcing steel fromcorrosion due to its highly alkaline nature. The high alkaline nature ofthe concrete causes a passive and noncorroding protective oxide film toform on steel. However, carbonation or the presence of chloride ionsfrom deicers or seawater can destroy or penetrate the film and result incorrosion. Corrosion-inhibiting admixtures chemically arrest thiscorrosion reaction. The materials most commonly used to inhibitcorrosion are calcium nitrite, sodium nitrite, sodium benzoate, certainphosphates or fluorosilicates, fluoroaluminites, amines and relatedchemicals.

Also of interest are dampproofing admixtures. Dampproofing admixturesreduce the permeability of concrete that have low cement contents, highwater-cement ratios, or a deficiency of fines in the aggregate. Theseadmixtures retard moisture penetration into dry concrete and includecertain soaps, stearates, and petroleum products.

Also of interest are gas former admixtures. Gas formers, or gas-formingagents, are sometimes added to concrete and grout in very smallquantities to cause a slight expansion prior to hardening. The amount ofexpansion is dependent upon the amount of gas-forming material used andthe temperature of the fresh mixture. Aluminum powder, resin soap andvegetable or animal glue, saponin or hydrolyzed protein can be used asgas formers.

Also of interest are permeability reducers. Permeability reducers areused to reduce the rate at which water under pressure is transmittedthrough concrete. Silica fume, fly ash, ground slag, natural pozzolans,water reducers, and latex can be employed to decrease the permeabilityof the concrete.

Also of interest are rheology modifying agent admixtures. Rheologymodifying agents can be used to increase the viscosity of cementitiouscompositions. Suitable examples of rheology modifier include firmedsilica, colloidal silica, hydroxyethyl cellulose, hydroxypropylcellulose, fly ash (as defined in ASTM C618), mineral oils (such aslight naphthenic), hectorite clay, polyoxyalkylenes, polysaccharides,natural gums, or mixtures thereof.

Also of interest are shrinkage compensation admixtures. The shrinkagecompensation agent which can be used in the cementitious composition caninclude but is not limited to RO(AO)₁₋₁₀H, wherein R is a C₁₋₅ alkyl orC₅₋₆ cycloalkyl radical and A is a C₂₋₃ alkylene radical, alkali metalsulfate, alkaline earth metal sulfates, alkaline earth oxides,preferably sodium sulfate and calcium oxide. TETRAGUARD® is an exampleof a shrinkage reducing agent and is available from BASF Admixtures Inc.of Cleveland, Ohio.

Bacteria and fungal growth on or in hardened concrete may be partiallycontrolled through the use of fungicidal and germicidal admixtures. Themost effective materials for these purposes are polyhalogenated phenols,dialdrin emulsions, and copper compounds.

Also of interest in certain embodiments are workability improvingadmixtures. Entrained air, which acts like a lubricant, can be used as aworkability improving agent. Other workability agents are water reducersand certain finely divided admixtures.

In certain embodiments, the cements of the invention are employed withfibers, e.g., where one desires fiber-reinforced concrete. Fibers can bemade of zirconia containing materials, steel, carbon, fiberglass, orsynthetic materials, e.g., polypropylene, nylon, polyethylene,polyester, rayon, high-strength aramid, (i.e. Kevlar®), or mixturesthereof.

The components of the settable composition can be combined using anyconvenient protocol. Each material may be mixed at the time of work, orpart of or all of the materials may be mixed in advance. Alternatively,some of the materials are mixed with water with or without admixtures,such as high-range water-reducing admixtures, and then the remainingmaterials may be mixed therewith. As a mixing apparatus, anyconventional apparatus can be used. For example, Hobart mixer, slantcylinder mixer, Omni Mixer, Henschel mixer, V-type mixer, and Nautamixer can be employed.

Following the combination of the components to produce a settablecomposition (e.g., concrete), the settable composition will set after agiven period of time. The setting time may vary, and in certainembodiments ranges from 30 minutes to 48 hours, such as 30 minutes to 24hours and including from 1 hour to 4 hours.

The strength of the set product may also vary. In certain embodiments,the strength of the set cement may range from 5 Mpa to 70 MPa, such as10 MPa to 50 MPa and including from 20 MPa to 40 MPa. In certainembodiments, set products produced from cements of the invention areextremely durable. e.g., as determined using the test method describedat ASTM C1157.

Aspects of the invention further include structures produced from thecements and settable compositions of the invention. Because thesestructures are produced from cements of the invention, they will includemarkers or components that identify them as being obtained from a waterprecipitated carbonate compound composition, such as trace amounts ofvarious elements present in the initial salt water source, e.g., asdescribed above. For example, where the mineral component of the cementcomponent of the concrete is one that has been produced from sea water,the set product will contain a seawater marker profile of differentelements in identifying amounts, such as magnesium, potassium, sulfur,boron, sodium, and chloride, etc.

Utility

The subject cements and settable compositions that include the same,find use in a variety of different applications, particularly asbuilding or construction materials. Specific structures in which thesettable compositions of the invention find use include, but are notlimited to: pavements, architectural structures, e.g., buildings,foundations, motorways/roads, overpasses, parking structures,brick/block walls and footings for gates, fences and poles. Mortars ofthe invention find use in binding construction blocks, e.g., bricks,together and filling gaps between construction blocks. Mortars can alsobe used to fix existing structure, e.g., to replace sections where theoriginal mortar has become compromised or erroded, among other uses.

Systems

Aspects of the invention further include systems, e.g., processingplants or factories, for producing the carbonate compound compositions,e.g., saltwater derived carbonate and hydroxide mineral compositions,and cements of the invention, as well as concretes and mortars thatinclude the cements of the invention. Systems of the invention may haveany configuration which enables practice of the particular productionmethod of interest.

FIG. 2 provides a schematic of a system according to one embodiment ofthe invention. In FIG. 2, system 100 includes water source 110. Incertain embodiments, water source 110 includes a structure having aninput for salt water, such as a pipe or conduit from an ocean, etc.Where the salt water source that is processed by the system to producethe carbonate compound composition is seawater, the input is in fluidcommunication with a source of sea water, e.g., such as where the inputis a pipe line or feed from ocean water to a land based system or ainlet port in the hull of ship, e.g., where the system is part of aship, e.g., in an ocean based system.

Also shown in FIG. 2, is CO₂ gaseous stream source 130. This source mayvary, e.g., such as an industrial plant gaseous stream source, etc., asdescribed above. The water source and the CO₂ gaseous stream source areconnected to the CO₂ charger and precipitator reactor 120. The chargerand precipitation reactor 120 may include any of a number of differentelements, such as temperature regulators (e.g., configured to heat thewater to a desired temperature), chemical additive elements, e.g., forintroducing chemical pH elevating agents (such as NaOH) into the water,electrolysis elements, e.g., cathodes/anodes, etc. This reactor 120 mayoperate as a batch process or a continuous process.

The product of the precipitation reaction, e.g., a slurry, is thenprocessed at a bulk dewatering station 140, as illustrated in FIG. 2.The dewatering station 140 may use a variety of different water removalprocesses, including processes such as continuous centrifugation,centrifugation, filter centrifugation, gravitational settling, and thelike.

The system shown in FIG. 2 also includes a drying station 160 for dryingthe dewatered precipitate produced at station 140. Depending on theparticular drying protocol of the system, the drying station 160 mayinclude a filtration element, freeze drying structure, oven drying,spray drying structure, etc., as described above in more detail.

Also shown is optional washing station 150, where bulk dewateredprecipitate from separation station 140 is washed, e.g., to remove saltsand other solutes from the precipitate, prior to drying at the dryingstation 160.

Dried precipitate from station 160 is then sent to refining station 180,where the precipitate may be mechanically processed and/or one or morecomponents may be added to the precipitate (e.g., as reviewed above) toproduce a final product.

As indicated above, the system may be present on land or sea. Forexample, the system may be a land based system that is in a coastalregion, e.g., close to a source of sea water, or even an interiorlocation, where water is piped into the system from a salt water source,e.g., ocean. Alternatively, the system may be a water based system,i.e., a system that is present on or in water. Such a system may bepresent on a boat, ocean based platform etc., as desired.

The following examples are put forth so as to provide those of ordinaryskill in the art with a complete disclosure and description of how tomake and use the present invention, and are not intended to limit thescope of what the inventors regard as their invention nor are theyintended to represent that the experiments below are all or the onlyexperiments performed. Efforts have been made to ensure accuracy withrespect to numbers used (e.g. amounts, temperature, etc.) but someexperimental errors and deviations should be accounted for. Unlessindicated otherwise, parts are parts by weight, molecular weight isweight average molecular weight, temperature is in degrees Centigrade,and pressure is at or near atmospheric.

EXPERIMENTAL

In the following example, the methodology used to produce a carbonateprecipitate from seawater (i.e., the P00099 precipitate), as well as thechemical and physical characteristics of the generated precipitate, aredescribed. In addition, the compressive strengths and shrinkageproperties of a blended cement made up of 80% ordinary Portland cement(OPC) and 20% P00099 are reviewed.

I. P00099 Precipitation Process

The following protocol was used to produce the P00099 precipitate. 380 Lof filtered seawater was pumped into a cylindrical polyethylene 60°-conebottom graduated tank. This reaction tank was an open system, leftexposed to the ambient atmosphere. The reaction tank was constantlystirred using an overhead mixer. pH, room temperature, and watertemperature were constantly monitored throughout the reaction.

25 g of granulated (Ca,Mg)O (a.k.a., dolime or calcined dolomite) wasmixed into the seawater. Dolime that settled to the bottom of the tankwas manually re-circulated from the bottom of the tank through the topagain, in order to facilitate adequate mixing and dissolution ofreactants. A second addition of 25 g of dolime was performed in anidentical manner, including a manual recirculation of settled reactant.When the pH of the water reached 9.2, a gas mixture of 10% CO₂ (and 90%compressed air) was slowly diffused through a ceramic airstone intosolution. When the pH of the solution fell to 9.0, another 25 g additionof dolime was added to the reaction tank, which caused the pH to riseagain. The additions of dolime were repeated whenever the pH of thesolution dropped to 9.0 (or below), until a total of 225 g were added. Amanual recirculation of settled reactant was performed in between eachdolime addition.

After the final addition of dolime, the continuous diffusion of gasthrough the solution was stopped. The reaction was stirred for anadditional 2 hours. During this time, the pH continued to rise. Tomaintain a pH between 9.0 and 9.2, additional gas was diffused throughthe reaction when the pH rose above 9.2 until it reached 9.0. Manualre-circulations of settled reactant were also performed 4 timesthroughout this 2 hour period.

2 hours after the final addition of dolime, stirring, gas diffusion andrecirculation of settled reactant was stopped. The reaction tank wasleft undisturbed for 15 hours (open to the atmosphere).

After the 15 hour period, supernatant was removed through the top of thereaction tank using a submersible pump. The remaining mixture wasremoved through the bottom of the tank. The collected mixture wasallowed to settle for 2 hours. After settling, the supernatant wasdecanted. The remaining slurry was vacuum filtered through 11 μm poresize filter paper, in a Büchner funnel. The collected filter cake wasplaced into a Pyrex dish and baked at 110° C. for 24 hours.

The dried product was ground in a ball mix and fractioned by sizethrough a series of sieves to produce the P00099 precipitate.

II. Materials Analysis

Of the different sieve fractions collected, only the fraction containingparticles retained on the 38 μm-opening sieve and passing through the 75μm-opening sieve was used.

A. Chemical Characteristics

The P00099 precipitate used for the blend were analyzed for elementalcomposition using XRF. Results for the main elements are reported forthe Quikrete type I/II Portland cement used in this blend as well as forthe P00099 precipitate. In Table 1, below.

TABLE 1 XRF analysis of the type I/II portland cement and P00099-002used in this blend CO₃ Na₂O MgO Al₂O₃ SiO₂ P₂O₅ SO₃ Cl K₂O CaO Fe₂O₃ Sr% Sample % % % % ppm % % % % % ppm diff. OPC1 2.15 1.95 4.32 20.31 23362.54 0.072 0.36 62.88 3.88 1099 0.002 P00099 1.36 3.44 0.14 0.083 4620.65 1.123 0.04 45.75 0.12 3589 46.82The XRD analysis of this precipitate indicates the presence of aragoniteand magnesium calcite (composition close to Mg_(0.1)Ca_(0.9)CO₃) and inminor amounts, brucite and halite (Table 2 and FIG. 3). The FT-IRanalysis of the P00099 precipitate confirms the presence of aragonite,calcite and brucite (FIG. 4).

TABLE 2 Magnesium Sample Aragonite Calcite Brucite Halite P00099 79.917.1 2.8 0.2The total inorganic carbon content measured by coulometry is in fairagreement with the same value derived from the XRD Rietveld estimatedcomposition coupled with XRF elemental composition. Table 3 provides acoulometric analysis of P00099 compared to % C derived from XRD/XRF data

TABLE 3 Total C derived from other analytical Total C from coulometrydata 10.93 ± 0.16% 11.5%B. Physical Characteristics

SEM observations (See FIGS. 5A and 5B) on the precipitate confirm thedominance of aragonite (needle-like) as well as the size of the particleagglomerates. The determined BET specific surface areas (“SSA”) of thePortland cement and the P00099 precipitate are given in Table 4.

TABLE 4 Type I/II Quikrete Portland cement P00099 1.18 ± 0.04 m²/g 8.31± 0.04 m²/g

The particle size distribution was determined after 2 min ofpre-sonication to dissociate the agglomerated particles. FIG. 6 providesa visual representation of the particle size distribution of the P00099precipitate.

III. OPC/P00099 Blended Cement

The P00099 precipitate was blended with ordinary Portland cement (OPC)by hand for approximately two minutes just before mixing the mortar. Theblended cement comprised 20% (w/w) P00099 and 80% (w/w) OPC.

A. Compressive Strengths

The compressive strength development was determined according to ASTMC109. Mortar cubes of 2″ side were used for the compression tests. Areplacement level of 20% was investigated for this precipitate andcompared to plain Portland type I/II cement mortars and to Portland typeI/II cement substituted by fly ash F. The water:cement ratio wasadjusted to 0.58 to meet the flow criterion of 110%+/−5% (value: 107%).

6 cubes were prepared for the blends. Changes to the ASTM C511 storageconditions were as follows:

-   -   The cubes were cured under a wet towel for 24 hours (estimated        relative humidity of 95%)    -   After demolding, the cubes were stored in the laboratory at a        relative humidity of 30-40% instead of the lime bath.

The results are shown in FIG. 7.

Data for a 5% replacement level was also investigated with a duplicateprecipitate (P00100, BET specific surface area of ca. 11 m²/g). Thewater:cement ratio was adjusted to 0.54 to meet the 110% flowrequirement. The results are summarized in FIG. 8. At a 5% level ofreplacement, the strength development is similar to that of plainPortland cement.

B. Shrinkage

The drying shrinkage of mortar bars at a replacement level of 20% wasinvestigated for the P00099 precipitate following ASTM C596. It wascompared to similar bars made with Portland cement type I/II only or ablend of Portland cement and fly ash F. The water:cement ratio wasadjusted to 0.58 to meet the flow criterion of 110%+/−5% (value: 107%).Changes to the ASTM C596 storage conditions were as follows: therelative humidity in the lab is closer to 30-40% than the 50%recommended by ASTM C596, increasing the drying potential. The resultsare shown in FIG. 9.

The P00099 mix was more prone to drying shrinkage than its plainPortland or Portland-fly ash counterparts due to the larger water:cementratio.

Approximate BET SSA Duration (weeks) Mix description composition W/C(m2/g) Flow 1 2 3 4 6 100% OPC baseline 0.40 1.2 105% 0.034% 0.052%0.056% 0.075% 80% OPC- 20% FAF1-1 0.40 0.59 118% 0.034% 0.054% 0.067%80% OPC - 20% P00099 80% aragonite 0.5 8.3 118% 0.043% 0.080% 0.099% 17%Mg-calcite <3% brucite <1% halite

Although the foregoing invention has been described in some detail byway of illustration and example for purposes of clarity ofunderstanding, it is readily apparent to those of ordinary skill in theart in light of the teachings of this invention that certain changes andmodifications may be made thereto without departing from the spirit orscope of the appended claims.

Accordingly, the preceding merely illustrates the principles of theinvention. It will be appreciated that those skilled in the art will beable to devise various arrangements which, although not explicitlydescribed or shown herein, embody the principles of the invention andare included within its spirit and scope. Furthermore, all examples andconditional language recited herein are principally intended to aid thereader in understanding the principles of the invention and the conceptscontributed by the inventors to furthering the art, and are to beconstrued as being without limitation to such specifically recitedexamples and conditions. Moreover, all statements herein recitingprinciples, aspects, and embodiments of the invention as well asspecific examples thereof, are intended to encompass both structural andfunctional equivalents thereof. Additionally, it is intended that suchequivalents include both currently known equivalents and equivalentsdeveloped in the future, i.e., any elements developed that perform thesame function, regardless of structure. The scope of the presentinvention, therefore, is not intended to be limited to the exemplaryembodiments shown and described herein. Rather, the scope and spirit ofpresent invention is embodied by the appended claims.

1. A settable composition comprising a hydraulic cement composition,wherein the hydraulic cement composition is a dry particulatecomposition comprising particles having an average particle size of 0.1to 100 microns, and wherein the hydraulic cement composition comprises acarbonate compound composition comprising carbon from a gaseous sourceof carbon dioxide, wherein the carbonate compound composition comprisesa metastable carbonate compound characterized by being more stable insalt water than in fresh water, wherein the metastable carbonatecomprises crystalline aragonite, and optionally vaterite or amorphouscalcium carbonate or combinations thereof, and wherein strontium ispresent in the carbonate composition in an amount ranging from 3 to10,000 ppm, wherein the strontium is present in the crystal lattice ofthe aragonite, wherein sodium is present in the carbonate composition inan amount less than 20,000 ppm, and wherein the settable composition,upon combination with water and setting and hardening, has a compressivestrength of 20-70 MPa.
 2. The settable composition of claim 1 whereinthe metastable carbonate composition comprises magnesium and calcium. 3.The settable composition of claim 1 wherein, upon combination withwater, the setting time of the composition is from 30 minutes to 48hours.
 4. The settable composition of claim 1 wherein said hydrauliccement composition has an average surface area from 0.5 m²/gm to 50m²/gm.
 5. The settable composition according to claim 1, wherein saidsettable composition further comprises a portland cement clinker, anaggregate, or a combination thereof.
 6. A building or constructionmaterial comprising a settable composition according to claim
 1. 7. Thebuilding material according to claim 6, wherein said building orconstruction material is a pavement or architectural structure isselected from the group consisting of: a building, foundation, amotorway, road, overpass, parking structure, brick, block, wall, footingfor a gate, fence or pole, and combinations thereof.